Quaternary ammonium salts and fabric coated therewith



United States Patent QUATERNARY AMMONIUM SALTS AND FABRIC COATED THEREWIT H John P. Conbere and Edward M. Perry, Barrington, R. L, assignors to Arnold, Hellman & Co., Incorporated, Providence, R. L, a corporation of Rhode Island No Drawing. Application October 21, 1957 Serial No. 691,150

11 Claims. (Cl. 117-1395) This application is a continuation-in-part of application Serial No. 608,187, filed September 6, 1956.

The present invention relates to novel quaternary ammonium compounds and methods of preparing the same.

An object of the invention is to provide novel quaternary ammonium salts of fatty acid esters of a polyhydroxypolyamine.

An additional object is to prepare novel compounds useful to impart softening and lubricating characteristics to textiles.

A further object is to prepare novel textile softeners havingincreased stability to heat.

. Yet another object is to prepare novel anti-static agents for textiles.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications Within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

In the parent application it has been disclosed that these objects can be attained by the preparation of quaternary ammonium salts of fatty acid esters of N,N,N', -tetrakis(2-hydroxyethyl) ethylenediamine having the formula noorncm omongon z or the formula ROCHrCEHn summon M-N-O HzCHrN-M 2X ROCHsCHn CHzCHsOR Z where R is an aliphatic acyl radical having 12 to 18 carbon atoms or hydrogen, at least one R being an aliphatic acyl radical, M is a monovalent hydrocarbon group containing 1 to 4 carbon atoms, X is an anion and Z is the valence of X.

R can be lauroyl, stearoyl, oleoyl, myristoyl, palmitoyl, ricinoleoyl, etc. M can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. X can be a sulfate ion, a halide in, e. g., chloride, bromide, iodide, benzene sulfonate 2,878,144 Patented Mar. 17, 195s "ice esters of polyhydroxyalkyl alkylene polyamines havingv the formulae:

RORi RiOR Z where R, M, X and Z are as defined above, R is an alkylene group having 2 to 4 carbon atoms, R is an alkylene group having 2 to 6 carbon atoms, and n is an integer from 1 to 3 with the further proviso that in For mula (a) and Formula (b) when R; is ethylene, at leastone of R, has 3 to 4 carbon atoms. The R groups can be the same or difierent. Similarly, when more than one R groups are present, they can be alike or different. The R, and R groups can be straight or branched chain. Thus, R, can be one of the groups CH CH CHr-(iT-CHr- CH: while B; can be OHsCIJHCHa CHs-(-CHzCHsCHr- When the R groups are not all alike, e. g., some 0 the groups are ethylene groups and the remainder are impropylene groups,,the average percentage of the two types of groups can be from 10 to of ethylene groups and from 90 to 10% of isopropylene groups.

The compounds of the present invention are valuable as softening and anti-static agents for textile fabrics such as cellulose acetate, nylon, vinyl resins, e. g., vinyl chloride resins, etc.

The compounds of the present invention lend valuable softening and lubricity to textile fabric and also prevent the undesirable physical manifestation of static electrical charges which tend to accumulate on many fibers. The compounds are water dispersible which results in easy and low cost application. The compounds also are unique in that they afiord a means of binding three or four long 'fatty acid chains, which when quaternized possess unexheat .(non-scorching) which is superior to the non-quaterq 3 niggd acetate salts of the same starting compound, for example. 4

The compounds of the present invention are made by reacting the appropriate tertiary amine with a quaternizing agent. As quaternizing agents, there can be employed alkyl halides, e. g., methyl bromide, methyl chloride, methyl iodide, ethyl bromide, propyl chloride, 11- hlut'yli chloride; dimethyl sulfate, dietliyl .sulfate, di-npropyl sulfate, di-n-butyl sulfate, methyl benzene sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, trimethyl phosphate, tri butyl phosphate, dimethyl butylphosphate trimethyl borate, allyl chloride, allyl bromide, crotyl' chloride, etc.

Whether the mono or diquaternary ammonium salt is formed depends on the proportions of the tertiary amine and the quaternizing agent. Two equivalents of quaternizing agent are required to form the diquaternary compound and only one equivalent to form the monoquaternary compound.

As illustrative compounds of the present invention, there can be rnentio'ned the monoquaternary ammonium salt prepared from N,N,N',N'-tetral(is(Z-hydioxyethyl) hexamethylenediamine monostearate and dimethyl sulfate, the corresponding salt from diethyl sulfate, the corresponding salt from methyl bromide, the corresponding saltfrom di-ti-butyl sulfate, the corresponding" saltfrom dinpropyl sulfate,j the corresponding salt from methyl the corresponding salt from methyl'bromide, the coi-responding'salt from methyl iodide, thecorriespond j salt from ethyl bromide, the correspondirigsalt'from r'i -propyl' bromide, the cprresponding salt from rig-butyl bromide, the corresponding salt from" isbutyl chloride, the; corresponding salt from tributyl phosphatd' the corrjes'ppndiug salt from trime'thyl' phosphate ythe' corresponding saltffrom trimethyl borate, the" corresponding salt from methyl benzenesulfonate, the corresponding salt from methyl p-tolue'nesulfonate. In place of the monoquaternary ammonium salt, there can be prepared the corresponding diquaternary compound, e: g:, the diquaternary ammonium salt prepared from N,N,N',N'- tetrakis(2 hydroxyethyl)-hexamethylenediamine monostearate and dimethyl sulfate. Similarly, there can be made the monoquaternary ammonium salt prepared from N,N,NZNf-tetrakisfi hydroxyethyl) hexamethyle nediamine distearate and dimethyl sulfate, as well as of the other quaternizing agents set forth supra. The diquaternary salt of this compounds, e. g., with dimethyl sulfate, also can be made. Likewise, there can be made the monoquaternary ammonium salt preparedfrorn N,N, NZNiet a sQ yd y h th s sd mi tristearate and dimethyl sulfate, as well as of the other quaternizing agents set forthsupra. The diquaternary salt of this compound, e. g., with dimethyl sulfate, also c a r be made. Additionally, there can be madethemonoquaternary ammonium salt prepared from N,N,NQN

tetrakis(2 hydroxyethyl) hexarnethylenedianrine tetrastearate and dimethyl sulfate, as well as'of s eamer .qnater'nizing agents set forth supra. The diquaternary salt of this compound, e. g., with dimethyl sulfate, also can'be' made.

Typical examples of other compounds within the presinvention include the monoquaternary ammonium ,sa tprepared. from N,N,N',N'-tetrakis(2 7 hydroxye'thyl) ti i'mthylenediamine trilaurate anddimethyl sulfate, as

ntras ate corresponding diquaterrrary ammonium salt,

thenionoquaternary ammonium salt prepared from N,N,

.NZNf-tetrakisQ hydroxypropyl) ethylenediamine tetraoleate and methyl bromide, the diquaternary ammonium salt frorn N,N'-di(2 hydroxyethyl) N,N-di(2' hydroxypropyl) ethylenediamine triricinoleate and methyl ptoluenesulfonate, the monoquaternary ammonium salt from N,N,N',N'-tetrakis(4 hydroxybutyl) ethylenediamine tristearate and dimethyl sulfate, the monoguaternary ammonium salt prepared from N,N,N, ,=N

penta (4 hydroxybutyl) diethylenetrianiine distearate and dimethyl sulfate, the diquaternary ammonium-sslt- It will be appreciated by those skilled in the art that mixed acylgroup containing compounds can likewise be" prepared'an'd that'the acyl group itself can be varied as indicated above.

The starting tertiary amines for the present invention are prepared by ester interchange between the appropriate hydroxyalkyl alkylene polyamine, e. g., N,N,N',N'- tetrakis(2 hydroxyethyl) hexamethylenediamine, and a lower alkyl ester of a higher fatty acid or fat acid. Mixed esters are prepared by using a mixture of esters, e. g., butyl stearate and butyl laurate in the ester interchange. The ester interchange is catalyzed by" alkaline earth and alkali metal hydroxide and alkoxides such as sodium hydroxide, sodium methoxide and also aluminum isopropoxide. The transes terificati'on"is carried out either with or without the aid of solvents such as toluene or xylene. The tertiary amine fatty acid esreiprpductsar'e oils or waxes. Increasing the number of acyl-g roups' in the molecule gives a harder wax. A

The hydroxyalkyl alkylene polyamine itself is'nor'nially prepared by reaction of the appropriate alkylene polyamine, e. g., ethylenediamine or hexamethylen'ediafnine or triethylene tetramine with the appropriate alklcne oxide or mixtures of alkylene oxides, e. g., ethylene oxide, propylene oxide, trimethylene oxide, butylerie oxide',; etc.

Illustrative examples showing the preparation of the materials of the present invention, aswell as of the starting materials, are given below;

' EXAMPLE 1 N,N,N,N-tc'tra kis (B hydroxyethyl) h'exa r'hethyle'ri'e'di amine-1,6 tristear'ate A mixture of 73 g. of N,N,N,N'-tetrakis(2- hydroxyethyl) hexarnethylenediamine-1,6 and 255 g. of n-butyl stearate were heated to C. under reduced pressure. The mixture was cooled to 50 C. and 1.2 g. sodium methylate added. The temperature was then increased, and butyl alcohol began to distill from the reaction mixture. The temperature was graduallyincreased to C. under reduced pressure. The charge was held at 140 C. for thirty minutes to remove the last traces of n-butyl alcohol. The product was a soft wax which contained 1.20 atoms of active hydrogen per mol.

EXAMPLE 2 N,N,N',N",N"-penta(Z-hydroxythyl) diethylene tria mine tristearate A stirred mixture of 81 g. of N,N,N',N,N"-penta(2- hydroxyethyl) diethylenetriamine and 255 g. of n-butyl stearate was heated to, 100 C. under reduced pressure. The mixture was cooled to 50 C. and 1.2 g. sodium methylate added. Heat was applied and butyl alcohol began to distill from the reaction mixture. The term perature was increased to 140 C. Heating was con tinned at 140 C. and under reduced pressure until butyl alcohol no longer distilled. The product was a soft wax.

EXAMPLE 3 I N ,N ,N i ,N -tetrakis(Z-hydroxypropyl ethylenediamine tristearate 73 g. of N,N,N';N'-tetrakis (2-hydroxypropyl) ethylenediamine .and 255. g..of.n-butyl stearatel were reactedeby thesanie procedure used in Example 2-to yield N,N,N,N'-'

tetrakis(2-hydroxyethyl) ethylenediamine tristearate, a very soft wax.

- EXAMPLE 4 N-(2-hydroxyethyl)-N,N,N'-tri(Z-hydroxypropyl) ethylenediamine tristearate In a similar manner to Example 2, 69.5 g. of N-(2- hydroxyethyl)-N,N,N'-tri(Z-hydroxypropyl) ethylenediamine was treated with 255 g. of n-butyl stearate to give N-(Z-hydroxyethyl)-N,N,N-tri(Z-hydroxypropyl) ethylenediamine tristearate, a very soft wax.

EXAMPLE 5 N,N,N',N-tetrakis( ,B-hydroxyethyl) propanediamine-1,2 tristearate In a manner similar to Example 2, 62.5. g. of N,N,N',N'- tetrakisw-hydroxyethyl) propanediamine-1,2 and 255 g. n-butyl stearate were reacted to give N,N,N',N'-tetrakis(fl-hydroxyethyl) propanediamine-1,2 tristearate as a hard wax.

EXAMPLE 6 N,N,N,N",N"',N"",N"-hepta(Z-hydroxyethyl) tetra- Y ethylenepentamine tetrastearate In a similar manner to Example 2, 124 g. of N,N,N, N",N",N"',N'"-hepta(2-hydroxyethyl) tetraethylenepentamine was treated with 340 g. of butyl stearate to give N,N,N',N",N,N",N" hepta(2 hydroxyethyl tetraethylenepentamine tetrastearate.

EXAMPLE 7 N,N,N',N",N"-penta(2-hydroxyethyl) diethylenetriamine pentastearate In a similar manner to Example 2, 81 g. of N,N,N',N", N"-penta(Z-hydroxyethyl) diethylenetriamineand 425 g. of butyl stearate were reacted to give N,N,N',N",N- penta(2-hydroxyethyl) diethylenetriamine pentastearate.

EXAMPLE 8 N,N,N,N-tetrak is( fi-hydroxyethyl) propanediamine-1,3

tristearate In a similar manner to Example 2, 62.5 g. of N,N,N', N-tetrakis(fi-hydroxyethyl) propanediamine-1,3 and 255 g. of butyl stearate were reacted to give N,N,N',N- tetrakis(B-hydroxyethyl) propanediamine-l,3 tristearate.

EXAMPLE 9 Tristearate ester of the amino alcohol formed from the reaction of ethylenediamine with 3.8 mols of ethylene oxide and .2 mol of propylene oxide In a. manner similar to Example 2, 59.8 g. of the amino alcohol formed from the reaction of one mol of ethylenediamine with 3.8 mols of ethylene oxide and .2 mol of propylene oxide was treated with 255 g. of butyl stearate to form the tristearate ester.

EXAMPLE 10 Irt'stearate ester of the amino alcohol formed from the reaction of ethylenediamine with 3.8 mols of propylene oxide and .2 mol of ethylene oxide In a similar manner to Example 2, 72.2 g. of the amino alcohol formed from the reaction of one mol of ethylenediamine with 3.8 mols of propylene oxide and .2 mol of ethylene oxide was reacted with 255 g. of butyl stearate to yield the tristearate ester.

EXAMPLE 11 ll lonoqttaternary ammonium salt prepared from N,N,N', v N-tetra kis(B-hydroxyethyl) hexamethylenediamine-L6 tristearate and dimethyl sulfate I I N,N,N',N'-tetrakis(B-hydroxyethyl) hexamethylenediamine-ueuist ara e 200, g.) was; heated to 100 0.

and 23.1 g. of dimethylsulfate' added with stirring during one hour. The temperature was maintained at C. for an additional hour. The product'was a hard wax which dispersed in water.

EXAMPLE 12 Monoquaternary ammonium salt prepared from N,N,N',

N", "-penta(2-hydroxyethyl) diethylenetriamine tristearate and dimethyl sulfate N,N,N',N,N" penta(2 hydroxyethyl) diethylenetriamine tristearate (200 g.) was, heated to 100 C. and 22.9 g. of dimethyl sulfate added during one hour with stirring. After the addition was complete, the whole was maintained at 100" C. for an additional hour. The product was a hard water dispersible wax.

EXAMPLE 13 Monoquaternary ammonium salt prepared from N,N,N,

N-tetrakis(Z-hydroxypropyl) ethylenediamine tristearate and dimethyl sulfate Dimethyl sulfate (23.1 g.) was added during one hour with stirring to 200 g. of N,N,N',,N'-tetrakis(Z-hydroxypropyl) ethylenediamine tristearate at 100 C. The temperature was maintained at "100 C. for one hour after the addition of the dimethyl sulfate was complete. The product was a hard wax which could be dispersed in water.

EXAMPLE 14 Monoquaternary ammonium salt prepared from N-(2- hydroxyethyl)-N,N',N'-tri(2-hydroxypropyl) ethylene diamine tristearate and dimethyl sulfate 2 200 g. I of N-(2-hydroxyethyl)-N,N',N'-tri(2-hydro propyl) ethylenediamine tristearate was heated to 100 C. and 23.4 g. of dimethyl sulfate added during one hour with stirring. The whole was held at 100 C. for one hour after the addition of dimethyl sulfate was complete. The product was a hard water dispersible wax.

EXAMPLE 15 Monoquaternary ammonium salt prepared from N,N. N,N' tetrakis([3 hydroxyethyl) pr0panediamine-1,2 and dimethyl sulfate 200 g. of N,N,N',N'-tetrakis(B-hydroxyethyl) propane. diamine-1,2 tristearate was heated to 100 C. and 24g. of dimethyl sulfate added during one hour. The temperature was maintained at 100 C. for an additional hour. The product was a hard wax which dispersed in water. 1

EXAMPLE 16 Monoquaternary ammonium salt prepared from NJV} N ,N ",N ,N ",N ""-hepta (Z-hydroxyethyl tetraethylenepentamine tetrastearate and dimethyl sulfate N,N,N',N",N"',N" ,N""-hepta(2-hydroxyethyl) tetraethylenepentarnine tetrastearate (200 g.) was heated to 100 C. and 16.1 g. of dimethyl sulfate added with stirring during one hour. The temperature was maintained at 100 C. for an additional hour. The product was a hard wax which dispersed in water.

EXAMPLE 17 I nxA-M'PLE 18 Mpnoijuat rniifyftzr'nntonium supplanted front 'N,'N,' 'N,N"-'tetrizkis(Z-hydrOXyethyZ) propanediamine-lj tristearate and dimethyl sulfate 200 g. of N,N,N',N '-tetrakis(2-hydroxyethyl) propanediaminelfi tristearate was heated to 100 C.,,and 24 g. of dimethyl sulfate added during one hour. The whole was maintained at 100 C. for one hour after the addition was complete. The product was a hard water dispersible wax. EXAMPLE 19 Man qsazerm human-q: mu prepared from diniethyZ sulfate and the tristejarate ester of the amino alcohol formed front-the, reaction of ethylenediamine with 3.8

mols of ethylene oxide and .2 Incl of propylene oxide Dimethyl sulfate (24.3 'g.) was added during one hour at 100 C. to 200 g. of the tristearateester of the amino alcohol formed from the reaction of ethylenediamine with 3.8 mols of ethylene oxide and .2 mol of propylene oxide. The temperature was maintained at 100 C. for one hour after the addition was complete. The product was a hard wax that dispersed in water.

EXAMPLE 20 Monoq'untrnnry ammonium salt prepared froindin ethyl sulfate iznd the tristearrzte ester of the amino alcohol formed from the reaction of ethylenediamine with 3.8 mols of propylene oxide and .2 mol of ethylene oxide 23.2 g. of dimethyl sulfate was added during one hour at .1005. C. to 200 of the tristearate ester of the amino alcohol formedfrom the, reaction of ethylenediamine with 3.8 mols of propylene oxide and .2 mol of ethylene oxide. After the additiodwas complete, the temperature was, maintained at l C. for one hour. The product was a hard wait that dispersed in water.

EXAMPLE 21 A 0.30% dispersion of the monoquaternary ammonium salt prepared from N,N,N,',N'-tetrakis(fi-hydroxyethyl) hexamethylenediamine-l,6 tristearate and dimethyl sulfate was applied to Nylon 200 taffeta in'a conventional padding machine at 120 F. in such a manner as to result in 50% pickup of the dispersion by the fabric. The fabric was dried at 225 F. The taffeta possessed improved softness to the 'hand, increased lubricity and superior anti-scorch and anti-static properties compared tountreated taffeta. 'Nylon 200 is a synthetic linear superpolyamide of the hexamethyleneadipamide type.

Unless otherwise stated, all parts and percentages are by weight. I l I v The examples of the parent application are set forth infra. .1 EXAMPLE 22.

N, I l,N,N'-tetrakis(Z-hydrokcyethyl) ethylenedidntine mono'stearate 2 Amixture of 472 of N ,N,N',N'-tetrakis(Z-hydroxy- I Ethyl) ethylene'diamine, 680 g. n-butyl stearate and 2.9 g. sodium hydroxide was stirred and heated to 110 C. at 70 mm. pressure. n-Butyl alcohol began to distill from the reaction mixture. Thc temperature was raised to 140 C. during an hour. The pressure was then reduced a to 17 mm. and the charge stirred at 140/ 17 mm. for one hour and fifteen minutes to remove the last traces of n-butyl alcohol. A total of 151 g. of butyl alcohol was collected (theory 148 g.). The product was a soft tan wax which contained 2.95 atoms of active hydrogen per 4 A stirred ar isss a l-l,N;N",

8 I hydroxyethyl) ethylenediamine, 204 g. of n-butylstearitis' and 0.7 g. of sodium hydroxide was heated to 120? C. at

mm. n-Butyl alcohol began to distill from the-reaction mixture. The temperature was raised to 140 C. during onehour.v The pressure was then reduced to 20 mm. and the charge stirred at 140 C. for one-half hour. A quantitative yield of product containing 2.0 atoms of active hydrogen per mol was obtained.

EXAMPLE 24 N,N,N',N-tetrakis(Z-hydroxyethyl) ethylenedia'mine tristearate EXAMPLE 25 N,N,N',N'-tetrakis(2-hya'rojcyethyl) ethylenediamine tetrastearate 236 g. of N,N,N',N'-tetrakis(2-hydroxyethyl) ethylene diamine, 1360 g. of n butyl stearate and 4 g. of sodium hydroxide were combined and treated by the same pro cedure used in Example 24 to yield N,N,N',N-tetrakis- (Z-hydroxyethyl) ethylenediamine tetrastearate, a softwax.

EXAMPLE 2s N,N,N',N'-tetrakis(Z-Iiydroxyethyl) ethylenetliamine dioleate In asimila r manner to Example 24, 11.8'g. of N,'N,-N', N'-tetrakis(Z-hydroxyethyl) ethylenediamine was treated with 33.8 g. of n-butyl oleate and 0.2 g. of sodium hydroxide to yield N,'N,N',N' -tetrakis(2-hydroxyethyl) ethylenediamine dioleate as a dark viscous liquid.

EXAMPLE 27 N,N,N',N'-tetrakis(Z-hydroxyethyl) ethylenediamine dilaurate In a similar manner to Example 24, 236 g. of N,N,N', N'-tetrakis(2-hydroxyethy1) ethylenediamine was treated with 512 g. n-butyl laurate and 1.9 g. of sodium hydroxide to yield N,N,N,N'-tet rakis(Z-hydroxyethyl) ethylenediamine dilaurate as a low melting wax.

The compounds of the present invention are prepared as follows:

EXAMPLE 28 Monoquaternary ammonium salt prepared from N,N,Nl,

N tetrakis(2 hydroxyethyl) ethylenediamine manosteamte and dimethyl sulfate N,N,N',Nf tetrakis (2 hydroxyethyl) ethylenediarnine monostearate (150.6 g.) was heated to C. and

37.8 g. of dimethyl sulfate added slowly with stirring.

The temperature wasmaintained between 100 C. and

C. and held therefor two hours. A soft wax,

easily dispersible in water, was obtained.

EXAMPLE 29 Monoquaternary ammonium salt prepared from N,N,N,

N tetrakis(2 hydroxyethyl) ethylenediamine monostearate and dimethyl sulfate in aqueous solution A stirred mixture of 72 g. of N,N,N,N' -tetrakis(2- hydroxyethyl) ethylenediamine monostearate and ml.

of water was heated to 100 C. and 18 g. 'ofdimethyl flea-sanctstunts was newly added. The mixture was heated at "some 2 e 9 e 100 C. for five hours and then cooled to'room temperature to yield a water dispersible product.

EXAMPLE 30 Monoquaternary ammonium salt prepared from N,N,N',

N tetrakis(2 hydroxyethyl) ethylenediamine m0n0- stearate and methyl toluenesulfonate N,N,N,N' tetrakis(2 hydroxyethyl) ethylenediamine monostearate (150.6 g.) was heated to 110' C. and 55.8 g. of methyl toluenesulfonate was slowly added with stirring. The temperature was increased to and maintained at 130 C. for four hours. A water dispersible product was obtained.

EXAMPLE 31 Monoquaternary ammonium salt prepared from N,N,N', N'-tetrakis(Z-hydroxyethyl) ethylenediamine distearate and dimethyl sulfate N,N,N',N' tetrakis(2 hydroxyethyl) ethylenediamine distearate (153.6 g.) was heated to 130 C. and 25.2 g. of dimethyl sulfate was slowly added. After the addition was complete, the whole was maintained at 130 C. for an additional hour and a half. The product was a water dispersible wax.

EXAMPLE 32 Diquaternary ammonium salt prepared from N,N,N', N'-tetrakis(Z-hydroxyethyl) ethylenediamine distearate and dimethyl sulfate 'Dimethyl sulfate (50.4 g.) was added slowly with stirring to 153.6 g. of N,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine distearate at 130 C. The heating was continued after the addition was complete for an additional two hours. The product was a hard wax and may be dispersed in water.

EXAMPLE 3 3 Monoquaternary ammonium salt prepared from N,N,N, N'-tetrakis(Z-hydroxyethyl) ethylenediamine distearate and methyl toluenesulfonate N,N,N',N' tetrakis(2 hydroxyethyl) ethylenediamine distearate (153.6 g.) was heated to 130 C., and 37.2 g. of methyl toluenesulfonate was slowly added with stirring. After the addition was complete, the mixture was heated for four hours at 130 C. The product was a water dispersible wax.

EXAMPLE 34 Monoquaternary ammonium salt prepared from N,N,N', N'-tetrakis(Z-hydroxyethyl) ethylenediamine distearate and methyl bromide Methyl bromide (17.8 g.) was added slowly to 143.5 g. of N,N,N,N'-tetrakis(Z-hydroxyethyl) ethylenediamine distearate. The addition was started at 63 C., and the mixture was heated to 120 C. during the addition and held at that temperature for an additional thirty minutes. A hard wax was formed that was easily dispersible in water.

EXAMPLE 35 10 EXAMPLE 3'6 Monoquaternary ammonium salt prepared from N,N,N', N'-tetrakis(Z-hydroxyethyl) ethylenediamine dilaurate and dimethyl sulfate 120 g. of N,N,N,N-tetrakis(Z-hydroxyethyl) ethylenediamine dilaurate was heated to 65 C. and 25.2 g. of dimethyl sulfate was slowly added with stirring. After all of the dimethyl sulfate had been added, the mixture was heated to 130 C. for three hours. The product was a low melting wax that formed a dispersion with water.

EXAMPLE 37 Monoquaternary ammonium salt prepared from N,N,N', '-tetrakis(2 hydroxyethyl) ethylenediamine dioleate and dimethyl sulfate 152.8 g. of N,N,N,N'-tetrakis(2-hydroxyethyl) ethyl-' enediamine dioleate was heated to 65 C., and 25.2 g. of dimethyl sulfate slowly added with stirring. After the addition was complete, the temperature was increased to and maintained at 130 C. for three hours. The product was a viscous liquid that formed a dispersion in water.

EXAMPLE 38 Monoquaternary ammonium salt prepared from N,N,N', N'-tetrakis(2hydr0xyethyl) ethylenediamine distearate and allyl chloride Allyl chloride (15.2 g.) was slowly added to 153 g. of N,N,N,N-tetrakis(Z-hydroxyethyl) ethylenediamine distearate which had been warmed to 60 C. After the addition was complete, the whole was heated at C. for one hour to yield the product as a soft, water dispersible wax.

EXAMPLE 39 Monoquaternary ammonium salt prepared from n-butyl bromide and N,N,N',N'-tetrakis(Z-hydroxj ethyl) ethylenediamine distearate n-Butyl bromide (27.4 g.) was added slowly to a stirred melt of 153 g. of N,N,N,N-tetrakis(2-hydroxyethyl) ethylenediamine distearate at 100 C. When the addition was complete, the reaction mixture was stirred and heated at C. for an additional three hours and thirty minutes. The product was a water dispersible wax.

EXAMPLE 40 Monoquaternary ammonium salt N tetrakis(2 hydroxyethyl) stearate and dimethyl sulfate Qimethyl sulfate (6.3 g.) was slowly added to 65 g. of N,N,N',N' tetrakis(2 hydroxyethyl) ethylenediamine tetrastearate at 100 C. After the addition was complete, the whole was stirred and heated at 100 C. for one hour to yield a water dispersible wax.

The quaternary ammonium salts of the present inven tion are water dispersible and possess surface active properties. They are easily applied to fabrics by the usual padding methods from aqueous dispersions. A typical example illustrating this use is as follows:

EXAMPLE 41 A 0.30% dispersion of the monoquaternary ammonium salt prepared from N,N,N,N'-tetrakis(2-hydroxyethyl) ethylenediamine distearate and dimethyl sulfate was applied to Nylon 200 taffeta by standard padding techniques, i. .e, a conventional padding machine, at 120 F. in such a manner as to result in 50% .pickup of the dispersion by the fabric. The fabric was dried at 225 F. Nylon 200 taffeta treated in this manner possessed improved softness to the hand, increased lubricity, and superior anti-scorch and antistatic properties. Nylon 200 is a synthetic linear superpolyamide of the hexamethyleneadipamide type.

ethylenediamine tetraprepared from N,N,N',

1-1 We claim: 1 l. A compound selected from the group consisting of I noR1 1ir-R, I;IR 'N R1o1i X ROB: \RXOR/n RiOR Z and i \i Roar-N4? N m -w nton 2xwhere R is selected from the group consisting of aliphatic acyl radicals containing from 12 to 18 carbon atoms and hydrogen, at least one R being said aliphatic'acyl radical;R is an'alkylene group having 2' to 4 carbon atoms, R: is an alkylene group having 2 to 6 carbon atoms, :1 is an integer from to 3 with the proviso that when n' is O and R; has 2 carbon atoms at least one R has 3 to 4 carbon atoms, M is' a' monovalent hydrocarbon grou containing 1 to 4 carbon atoms, X is an anion selected from the group consisting of chloride, bromide, iodide, sulfate, benzene s'ulfonate, toluene sulfonate, phosphate and borate and Z is'the valence of X.

2. A compound as'recited in claim 1 wherein at least one R is a stearoyl radical.

1 3; A compound as in claim 1 wherein a saturated Hydrocarbon group;

4. A compound as in claim 3 wherein X is a sulfate'ion. I v 5. A- compound as in claim 1 wherein-at least one' R is-a' stearoyl radicaL M is asaturated hydrocarbon group and X'is asulfate ion.

'6. A quaternary ammonium-salt ofaco mpound-having the formula Where'R is selectedfrom the group'consisting of aliphatic acyl radicals containing from 12 to 18c'arbonatoms and hydrogen, at least one R being said aliphatic acyl radical, where n is an integer from 3 to 6 and the quaternizing' group is a monovalent hydrocarbon group. containing 1 to 4 carbon atoms and an anion selected from the group consistingof' chloride, bromide, iodide, sulfate, benzene sulfonat'e, toluene sulfonate, phosphateand borate.

(ROCHrCHzhNCHzCHKNCHrCHi )N(GH2CH1OR): onionron phatic acyl radicals containing from 12 to 18 carbon 12 atoms andvhydrogen, at least one Rbeing said aliphatic acyl radical, where his an integer from 1 to 3 and quaternizing group is a monoval'ent hydrocarbon group containing 1 to 4 carbon atomsand an anion selected from the group consisting of chloride, bromide, iodide, sulfate, benzene sulfonate, toluene sulfonate, phosphate and b'orat'e.

8. A quaternary ammonium salt of a compound having the formula Ra no'omonnncomrrmomomon where R is selected from the group consisting of all phatic acyl radicals containing from 12 to 18 carbon atoms and hydrogen, at least one R being said aliphatic acyl radical, and R is an alkyl group containing 1 to 4 carbon atoms and the quateruizing group is,a mono: valiant-hydrocarbon group containing 1 to 4 carbon atoms and an anion selected from the group consisting of chloride, bromide, iodide, sulfate, benzene sulfonate, toluene sulfonate, phosphate and borate.

9. A quaternary amornnium salt of a' compound having the formula where R is selected from the group consisting of all phatic acyl radicals containing from 12 to 18 carbon atoms and hydrogemat' least one R being said aliphatic. acyl radical, R is selected from the group consisting-of hydrogen and an alkyl group having 1 to 2 carbon atoms, at leastone R beingsaid alkyl group, n is an integer from 2 to' 6 and the quaternizing group isa monovalent hydrocarbon group containing l to 4 carbon'atoms and an anion selected from the group consisting of chloride, bromide, iodide, sulfate, benzene sulfonate, toluene sulfonate', phosphate and borate.

10. A process of preparing a compound set forth in claim 1 comprising reacting a compound having the formula ROR: v \RlOR/n RIOR with a conipound having the formula M X. I p I 11. A textile fabric having improved softness and antistatic properties coated with the product of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2;71 9,'156 DeBenneville' etal Sept. 17, 1955" 

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF
 11. A TEXTILE FABRIC HAVING IMPROVED SOFTNESS AND ANTISTATIC PROPERTIES COATED WITH THE PRODUCT OF CLAIM
 1. 